JP2019104824A - Resin composition, method for producing resin composition, and molded body - Google Patents

Abstract

To provide a resin composition which is excellent in flowability and appearance and has high-level flame retardancy, a method for producing a resin composition, and a molded body.SOLUTION: A resin composition contains (a) a polyphenylene ether resin, (b) a styrene resin, (c) a phosphorus compound, (d) an inorganic filler and (e) polytetrafluoroethylene, in which when a test piece of a resin composition which contains 35-60 mass% of the component (d) in the resin composition and is prepared on sizes of a length in a flow direction of 125 mm, a length in a vertical direction of 13 mm and a thickness of 1.6 mm is aged on conditions of a temperature of 150°C and 24 hours, a shrinkage ratio of the test piece represented by following expression is 6-20%. Test piece shrinkage ratio [%]=((length of test piece in flow direction before aging [mm]-length of test piece in flow direction after aging [mm])/(length of test piece in flow direction before aging [mm]))×100.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a method of producing a resin composition, and a molded body.

  Heretofore, polyphenylene ether resins are widely used in home appliances / OA devices, automobile parts and the like because they have heat resistance, hydrolysis resistance and flame retardancy in addition to excellent electrical insulating properties.

  For these applications, high flame retardancy is required due to fire problems etc., and polyphenylene ether resins can be easily obtained by adding phosphorus compounds without using halogen compounds. . In addition, since higher rigidity, heat resistance, and dimensional properties are required, reinforced resin compositions containing an inorganic filler have come to be widely used.

  In general, when an inorganic filler is blended, flame retardancy, fluidity and appearance deteriorate. With regard to flame retardancy in particular, in recent years, even more severe levels of flame retardancy have started to be required. In addition, with the progress of miniaturization of parts and complexity of structure, these materials are often molded with thin-walled materials, and therefore, it is also required to have good fluidity (molding processability) at the time of injection molding. ing.

  In order to meet the above requirements, a polyphenylene ether-based resin composition is conventionally disclosed which is blended with a styrene-acrylonitrile copolymer and has excellent balance of fluidity, mechanical properties, etc., and flame retardancy (for example, Patent Document 1).

JP-A-9-31321

  However, the resin material disclosed in Patent Document 1 also has room for further improvement from the viewpoint of achieving the high level of flame retardancy that has recently been required.

  Therefore, in the present invention, it is an object of the present invention to provide a resin composition which is excellent in fluidity and appearance and has a high level of flame retardancy, a method of producing the resin composition, and a molded body.

  As a result of earnestly examining in order to solve the above-mentioned subject, content and heat of an inorganic filler are explained to a resin composition containing polyphenylene ether system resin, a styrene system resin, a phosphorus system compound, an inorganic filler, and polytetrafluoroethylene. By controlling the thermal contraction rate after aging within a specific range, it has been found that excellent fluidity, appearance and high level of flame retardancy can be obtained, and the present invention has been completed.

  That is, the present invention is as follows.

[1]
(A) polyphenylene ether resin,
(B) styrenic resin,
(C) phosphorus compounds
(D) inorganic filler,
(E) polytetrafluoroethylene,
A resin composition containing
The resin composition contains 35 to 60% by mass of the component (d),
When the test piece of the resin composition prepared with dimensions of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness is aged at a temperature of 150 ° C. for 24 hours, The resin composition, wherein the shrinkage factor of the test piece to be shown is 6 to 20%.
Specimen shrinkage factor [%] = ((Length of specimen in flow direction before aging [mm]-Length of specimen in flow direction after aging [mm]) / (specimen in flow direction before aging Length [mm])) × 100
[2]
With respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c),
50 to 70 parts by mass of the component (a),
10 to 30 parts by mass of the component (b),
The resin composition as described in [1] which contains 10-30 mass parts of said (c) components, and 0.05-1 mass part of said (e) components.
[3]
The component (a) is
(A-1) a polyphenylene ether resin having a reduced viscosity of 0.45 to 0.55 dL / g,
(A-2) a polyphenylene ether resin having a reduced viscosity of 0.35 to 0.45 dL / g,
Including
The resin according to [1] or [2], wherein the content of the component (a-2) is 60 to 90 parts by mass with respect to a total of 100 parts by mass of the component (a-1) and the component (a-2) Composition.
[4]
The resin composition in any one of [1]-[3] whose said (d) component is 1 or more types chosen from glass fiber and mica.
[5]
The resin composition in any one of [1]-[4] whose said (c) component is a condensation phosphoric acid ester compound.
[6]
The molded object characterized by including the resin composition in any one of [1]-[5].
[7]
It is a manufacturing method of the resin composition in any one of [1]-[5],
A method for producing a resin composition, comprising the step of melt-kneading the components (a) to (e) using an extruder.
[8]
Including the step of dry blending the powdered polytetrafluoroethylene of the component (e) and / or the modified polytetrafluoroethylene with at least one of the components (a) to (d) and supplying it to the extruder , The manufacturing method of the resin composition as described in [7].
[9]
In the feeding step, dry blending of the powdered polytetrafluoroethylene and / or modified polytetrafluoroethylene of the component (e) with all or part of the component (a) is fed to the extruder. The manufacturing method of the resin composition as described in [8] which contains these.

  According to the present invention, it is possible to provide a resin composition excellent in flowability and appearance and having a high level of flame retardancy, a method for producing the resin composition, and a molded body.

FIG. 1 is a schematic view showing a screw configuration of a twin-screw extruder used in Examples and Comparative Examples, and a set temperature of a barrel.

  Hereinafter, modes for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following present embodiment is an illustration for describing the present invention, and the present invention is not limited to the following embodiment. In addition, the present invention can be appropriately modified and implemented within the scope of the present invention.

<Resin composition>
The resin composition of the present invention comprises (a) a polyphenylene ether resin, (b) a styrene resin, (c) a phosphorus compound, (d) an inorganic filler, and (e) polytetrafluoroethylene. The resin composition contains 35 to 60% by mass of the component (d), and has a length of 125 mm in the flow direction, a length of 13 mm in the vertical direction, and a thickness of 1.6 mm. The test piece of the resin composition is characterized in that the shrinkage of the test piece is 6 to 20% when it is aged at a temperature of 150.degree. C. for 24 hours.
The contraction rate is more preferably 7 to 18%, further preferably 7 to 15%.
The said shrinkage | contraction rate is excellent in drip prevention property at the time of combustion by being 6% or more, an external appearance, and is excellent in fluidity | liquidity and a flame retardance by being 20% or less.

<Shrinkage percentage of resin composition>
In the present disclosure, “aging” refers to placing in a high temperature state for a certain period of time, with a temperature of 150 ° C. and a time of 24 hours.
Test pieces of the resin composition can be prepared from the dried resin composition pellets using an injection molding machine, and have a length of 125 mm in the flow direction, a length of 13 mm in the vertical direction, and a thickness of 1.6 mm. .
In the present disclosure, “flow direction” refers to the direction (MD) in which the resin composition flows when injection molding the resin composition, and “vertical direction” refers to the width direction perpendicular to the “flow direction”. Say (TD).

The shrinkage rate (%) of the test piece can be determined from the following equation.
Specimen shrinkage factor [%] = ((Length of specimen in flow direction before aging [mm]-Length of specimen in flow direction after aging [mm]) / (specimen in flow direction before aging Length [mm])) × 100

The shrinkage factor of the test piece is 6 to 20%, more preferably 7 to 18%, still more preferably 7 to 15%. The said shrinkage | contraction rate is excellent in drip prevention property at the time of combustion by being 6% or more, an external appearance, and is excellent in fluidity | liquidity and a flame retardance by being 20% or less.
In addition, the contraction rate of the test piece of a resin composition can be specifically measured by the method as described in the below-mentioned Example.

As a method of increasing the shrinkage rate of the test piece after aging, for example, the content of the component (e) in the resin composition is increased, the dispersibility of the component (e) is increased, and the fibril structure of the component (e) is The increase etc. are mentioned.
Conversely, as a method of lowering the shrinkage rate, for example, the content of the component (e) in the resin composition is reduced, the dispersibility of the component (e) is reduced, the fibril structure of the component (e) is reduced, etc. It can be mentioned.

Moreover, when the screw rotation speed of the extruder increases, the dispersibility of the component (e) is increased, but the fibril structure of the component (e) is easily broken. Conversely, when it is lowered, the dispersibility of the component (e) is decreased. Since the fibril structure of the component e) is less likely to break, the screw rotational speed is appropriately adjusted to adjust the contraction rate.
With regard to the screw configuration, if the kneadability is high, the dispersibility of the component (e) is increased, but the fibril structure of the component (e) is easily broken, and if the kneadability is low, the dispersion of the component (e) is dispersed. Although the property is lowered, the fibril structure of the component (e) is hardly broken. Therefore, the screw configuration is appropriately adjusted to adjust the contraction rate.

  Thus, the shrinkage ratio is determined by the content of the components (a) to (e) in the resin composition, the blending method of the raw materials, the method of feeding the raw materials into the extruder, screw configuration, and the extruder of the kneading step. It can adjust with the rotation speed of a screw, kneading temperature, etc.

-(A) polyphenylene ether resin-
(A) The polyphenylene ether resin (sometimes referred to herein as "PPE" or sometimes simply referred to as "(a) component") may be a homopolymer (homopolymer) of phenylene ether And copolymers of phenylene ether with other monomers.
As the component (a), one type may be used alone, or two or more types may be used in combination.

［式中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜７の第１級のアルキル基、又は炭素数１〜７の第２級のアルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群より選ばれる一価の基を表す。］ Examples of the component (a) include homopolymers and / or copolymers having a repeating unit structure (a unit structure derived from phenylene ether) represented by the following formula (1).

[Wherein, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, a C 1-7 primary alkyl group, or a C 1-7 It is selected from the group consisting of a secondary alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, and a halohydrocarbon oxy group in which at least two carbon atoms separate a halogen atom from an oxygen atom. Represents a monovalent group. ]

  Examples of the component (a) include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-). Homopolymers such as 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and other phenols (e.g. And copolymers thereof with 6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4-phenylene ether) Is more preferred.

  A conventionally known method can be applied to the method for producing the component (a). As a method of producing the component (a), for example, a method of producing by oxidatively polymerizing 2,6-xylenol or the like using a complex of a cuprous salt and an amine as a catalyst, JP-A-50-150798. And the methods described in JP-A-50-051197 and JP-A-63-152628.

  The reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C., measured with a Ubbelohde viscosity tube) of the component (a) is preferably 0.7 dL / g or less from the viewpoint of fluidity, 0 It is more preferably 0.2 dL / g or less, preferably 0.2 dL / g or more, and more preferably 0.3 dL / g or more from the viewpoint of preventing dripping.

  As said (a) component, you may mix and use two or more polyphenylene ethers from which a reduced viscosity differs. From the viewpoint of the balance between the fluidity and the dripping prevention property at the time of combustion, the component (a) has a (a-1) reduced viscosity of 0.45 to 0.55 dL / g, preferably 0.48 to 0. .53 dL / g of polyphenylene ether resin and (a-2) a polyphenylene ether resin having a reduced viscosity of 0.35 to 0.45 dL / g, preferably 0.38 to 0.43 dL / g, It is preferable that the content of the component (a-2) is 60 to 90 parts by mass, more preferably 65 to 80 parts by mass, based on 100 parts by mass of the components (a-1) and (a-2). It is.

The component (a) may contain a modified polyphenylene ether which is wholly or partially modified.
The modified polyphenylene ether referred to herein has at least one carbon-carbon double bond and / or triple bond in the molecular structure and is composed of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group and a glycidyl group. It refers to a polyphenylene ether modified with a modifying compound having at least one group selected from the group (hereinafter sometimes referred to simply as "modifying compound"). The modifying compounds may be used alone or in combination of two or more.

  The method for producing the above-mentioned modified polyphenylene ether is not limited to the following. For example, (1) a range of 100 ° C. or more and less than the glass transition temperature of polyphenylene ether in the presence or absence of a radical initiator Method of reacting polyphenylene ether and modifying compound without melting polyphenylene ether at temperature, (2) Melt kneading of polyphenylene ether and modifying compound at a temperature in the range of glass transition temperature of polyphenylene ether to 360 ° C. And (3) a method in which polyphenylene ether and a modifying compound are reacted in a solution at a temperature lower than the glass transition temperature of polyphenylene ether, and any of these methods may be used, but the viewpoint of productivity From the above, the method of (1) or (2) is preferable.

  Next, the above-mentioned modifying compound used for producing modified polyphenylene ether will be described.

Examples of the modifying compound having a carbon-carbon double bond and having a carboxylic acid group and / or an acid anhydride group include, for example, maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2- Examples thereof include dicarboxylic acids and acid anhydrides thereof.
Among them, maleic acid, fumaric acid and maleic anhydride are preferable, and fumaric acid and maleic anhydride are more preferable, from the viewpoint of reactivity with the polyphenylene ether resin. Also, compounds in which one or two of the two carboxyl groups of these unsaturated dicarboxylic acids are esterified can be used as the modifying compound.

Examples of the modifying compound having a carbon-carbon double bond and a hydroxyl group include, for example, a general formula C _n H _{2 n-1} OH (n is a positive integer) such as allyl alcohol and 4-penten-1-ol. unsaturated alcohols represented, 1,4-pentadiene-3-unsaturated alcohol (n is a positive integer of 2 or more) general formula C _n H _2n-3 OH in ol represented by the general formula C _n H Unsaturated alcohol represented by _2n-5 OH (n is a positive integer of 3 or more), unsaturated alcohol represented by C _n H _2n-7 OH (n is a positive integer of 4 or more), and the like can be mentioned. .

  Examples of the modifying compound having a carbon-carbon double bond and a glycidyl group include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural fat and the like, and the like. Among them, glycidyl acrylate and glycidyl methacrylate are preferable.

  0.1-10 mass parts is preferable with respect to 100 mass parts of polyphenylene ethers, and, as for the addition amount of the modification compound at the time of manufacturing modified polyphenylene ether, 0.3-5 mass parts is more preferable, and 0.5-3 Parts by weight are more preferred. If it is 0.1 mass part or more, the effect by modification | denaturation of polyphenylene ether is easy to express, and if it is 10 mass parts or less, the side effect by modification | denaturation does not express easily.

  The amount of the radical initiator to be added when producing a modified polyphenylene ether using a radical initiator is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0 based on 100 parts by mass of the polyphenylene ether. 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass. If it is 0.001 mass part or more, it is excellent in modification efficiency. Moreover, if it is 1 mass part or less, low molecular-weight-izing of modified | denatured polyphenylene ether does not occur easily, and it is excellent in the balance of a modification rate and a physical property.

  In addition, the addition ratio of the modified compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0. It is 1 to 1% by mass. The remaining amount of unreacted modified compound and / or polymer of modified compound in the modified polyphenylene ether is preferably less than 5% by mass, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

  The content of the component (a) in the resin composition of the present embodiment is 100 parts by mass in total of the components (a), (b) and (c) from the viewpoint of balance of fluidity and flame retardancy. It is preferable that it is 50-70 mass parts, More preferably, it is 55-70 mass parts, More preferably, it is 60-70 mass parts.

-(B) Styrene resin-
The styrene resin (b) in the present embodiment (sometimes referred to simply as “component (b)” in the present specification) may be a styrene compound or a copolymer copolymerizable with a styrene compound and a styrene compound. It is a polymer obtained by polymerizing a compound in the presence or absence of a rubbery polymer.
(B) A styrene resin may be used individually by 1 type, and may mix and use 2 or more types.

（式中、Ｒは水素、低級アルキル基又はハロゲンを示し、Ｚはビニル基、水素、ハロゲン及び低級アルキル基よりなる群から選択され、ｐは０〜５の整数である。） The styrenic compound means a compound represented by the following formula (2).

(Wherein R represents hydrogen, lower alkyl group or halogen, Z is selected from the group consisting of vinyl group, hydrogen, halogen and lower alkyl group, and p is an integer of 0 to 5).

  Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like, among which styrene is preferable.

Moreover, as a compound copolymerizable with a styrenic compound, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride and the like are mentioned. Used together with styrenic compounds. Among these, acrylonitrile is preferable.
The amount of the compound copolymerizable with the styrenic compound is preferably 20% by mass or less, more preferably 15% by mass or less based on the total amount of the styrenic compound and the compound copolymerizable with the styrenic compound.

  Further, as the rubbery polymer, conjugated diene rubber, copolymer of conjugated diene and aromatic vinyl compound, hydrogenated product thereof, ethylene-propylene copolymer rubber, etc. may be mentioned. Among them, partially hydrogenated polybutadiene having a degree of unsaturation of 80 to 20%, and polybutadiene containing 90% or more of a 1,4-cis bond are more preferable.

  (B) As a styrene resin, polystyrene, rubber-reinforced polystyrene (high impact polystyrene (HIPS)), styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), other styrenes Examples include copolymer and the like. Particularly preferred is a combination of polystyrene and rubber-reinforced polystyrene using polybutadiene containing 90% or more of 1,4-cis bonds. In addition, homopolystyrene is also preferable, and either atactic polystyrene or syndiotactic polystyrene can be used.

  The content of the component (b) in the resin composition of the present embodiment is 100 parts by mass in total of the components (a), (b) and (c) from the viewpoint of flame retardancy and fluidity balance. It is preferable that it is 10-30 mass parts, More preferably, it is 10-25 mass parts, More preferably, it is 10-20 mass parts.

-(C) phosphorus compound-
The resin composition of the present embodiment contains (c) a phosphorus-based compound (sometimes referred to simply as “component (c)” in the present specification).
As the component (c), one type may be used alone, or two or more types may be used in combination.

As the component (c), any phosphorus-containing flame retardant known in the art such as organic phosphorus compounds, red phosphorus, and inorganic phosphates can be used. Among these, phosphoric acid ester compounds are preferable.
Examples of the component (c) include, but are not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, triphenyl phosphate, and the like. Phosphoric ester compounds such as cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethylethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc .; Modified phosphoric acid ester compounds; and various condensed type condensed phosphoric acid ester compounds. Among these, condensed phosphoric acid ester compounds are preferable.

［式（３）中、Ｑ⁴¹、Ｑ⁴²、Ｑ⁴³、及びＱ⁴⁴は、各々独立して、炭素原子数１〜６のアルキル基であり；Ｒ⁴¹、及びＲ⁴²は、メチル基であり；Ｒ⁴³、及びＲ⁴⁴は、各々独立して、水素原子又はメチル基であり；ｘは、０以上の整数であり；ｐ₁、ｐ₂、ｐ₃、及びｐ₄は、それぞれ、０〜３の整数であり；ｑ₁、及びｑ₂は、それぞれ、０〜２の整数である］

［式（４）中、Ｑ⁵¹、Ｑ⁵²、Ｑ⁵³、及びＱ⁵⁴は、各々独立して、炭素原子数１〜６のアルキル基であり；Ｒ⁵¹は、メチル基であり；ｙは、０以上の整数であり；ｒ₁、ｒ₂、ｒ₃、及びｒ₄は、それぞれ、０〜３の整数であり；ｓ₁は、０〜２の整数である］ As said condensed phosphoric acid ester type compound, what contains at least 1 sort (s) chosen from the group which consists of condensed phosphoric acid ester represented by following formula (3) and following formula (4) as a main component is preferable.
The term "main component" as used herein means that the content of at least one selected from the group consisting of aromatic condensed phosphoric esters represented by the following formula (3) and the following formula (4) is (c) component 100 It means that 90 mass% or more is contained with respect to mass%, Preferably it is 95 mass% or more, More preferably, it is 100 mass%.

[In formula (3), Q ⁴¹ , Q ⁴² , Q ⁴³ and Q ⁴⁴ are each independently an alkyl group having 1 to 6 carbon atoms; and R ⁴¹ and R ⁴² are methyl groups. R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or a methyl group; x is an integer of 0 or more; p ₁ , p ₂ , p ₃ and p ₄ are each 0 to 10 It is an integer of 3; q ₁ and q ₂ are each an integer of 0 to 2]

[In formula (4), Q ⁵¹ , Q ⁵² , Q ⁵³ and Q ⁵⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁵¹ is a methyl group; y is R ₁ , r ₂ , r ₃ and r ₄ are each an integer of 0 to 3; s ₁ is an integer of 0 to 2]

  In addition, the condensation phosphoric acid ester compound represented by said Formula (3) and said Formula (4) may contain multiple types of molecules, respectively. Moreover, it is preferable that x of Formula (3) and y of Formula (4) are an integer of 1-3.

Among them, as component (c), condensed phosphorus in which R ⁴³ and R ⁴⁴ in the formula (3) represent a methyl group, and p ₁ , p ₂ , p ₃ , p ₄ , q ₁ and q ₂ are 0 Acid ester, Q ⁴¹ , Q ⁴² , Q ⁴³ , Q ⁴⁴ , R ⁴³ and R ⁴⁴ in the formula (3) represent a methyl group, q ₁ and q ₂ are 0, p ₁ , p ₂ , p ₃ And p ₄ is an integer of 1 to 3 and at least 50% by mass with respect to 100% by mass of the component (c), wherein x is an integer of 1 to 3 (particularly, x is 1) Is preferred. By using these condensed phosphoric acid ester compounds, the volatility of the resin composition during molding can be further reduced.

  The content of the component (c) in the resin composition of the present embodiment is the component (a), the component (b), and the component (c) from the viewpoints of mechanical physical properties and heat resistance and balance of fluidity and flame retardancy. It is preferable that it is 10-30 mass parts with respect to a total of 100 mass parts, More preferably, it is 10-25 mass parts, More preferably, it is 15-25 mass parts.

-(D) Inorganic filler-
Glass fibers, glass flakes, mica, wollastonite as the (d) inorganic filler (sometimes referred to simply as “component (d)” in the present specification) contained in the resin composition of the present embodiment , Talc, calcined clay and the like. Glass beads and glass flakes when low dimensional anisotropy is required, glass fibers and whiskers when high rigidity and high impact resistance are required, and metal fibers for the purpose of conductivity It is preferable to select and use iron oxide when high specific gravity is required. It is preferable that it is 1 or more types chosen from glass fiber and mica from a viewpoint of mechanical physical properties and a flame retardance, and it is more preferable that it is glass fiber and mica.
The component (d) may be used alone or in combination of two or more, and may be surface treated with a silane coupling agent as desired, as long as the object of the present invention is not impaired. Or, those subjected to focusing treatment with a focusing agent can be used.

  The content of the component (d) in the resin composition of the present embodiment in the resin composition is 35 to 60% by mass, preferably 35 to 55%, from the viewpoint of balance of fluidity and mechanical physical properties and dimensional characteristics. %, More preferably 40 to 50% by mass.

-(E) polytetrafluoroethylene-
The (e) polytetrafluoroethylene (in the present specification, sometimes referred to simply as “component (e)”) (PTFE) of the present embodiment can be used as a drip by forming a fibril structure in polyphenylene ether. It has a high inhibitory effect and is suitable as a drip inhibitor.

Examples of the component (e) include homopolymers of tetrafluoroethylene and copolymers of tetrafluoroethylene with difluoroethylene, trifluoroethylene, hexafluoropropylene and the like, and only one of them may be used alone. They may be used in combination of two or more.
Among them, it is preferable to use 10 to 90% by mass, preferably 15 to 70% by mass of PTFE, and to use modified PTFE whose handleability is improved by another resin. Such modified PTFE is described, for example, in Japanese Patent Application Laid-Open Nos. 09-95583 and 11-29679, and as a product, trade names of metabrene (Mitsubishi Rayon Co., Ltd.) and BLENDEX 449 (Chemcula Co., Ltd.) Are sold at.

As a form of addition to the resin composition of PTFE, any powder or dispersion may be used as long as it can take the form of PTFE in the resin composition as in the present embodiment. Moreover, the method of adding PTFE, after producing a masterbatch by (a) polyphenylene ether type-resin or other resin etc. is also considered.
In the case of the PTFE masterbatch, heat is applied twice when producing the masterbatch and when producing the resin composition. It is preferable to obtain the resin composition by one-time extrusion from the viewpoint of obtaining excellent drip-preventing property at the time of combustion and appearance.
More preferably, it is preferable to use powder PTFE and / or modified PTFE, and to dry blend at least one component of the components (a) to (d) in advance with the PTFE and supply it to the extruder. In particular, it is preferable to dry blend the whole or a part of the (a) polyphenylene ether resin with the PTFE in advance and supply it to the extruder.

  The content of the component (e) in the resin composition of the present embodiment is that of the components (a), (b), and (c) from the viewpoints of fluidity and flame retardancy and balance between dripping prevention during combustion. It is preferable that it is 0.05-1 mass part with respect to a total of 100 mass parts, More preferably, it is 0.1-0.8 mass part, More preferably, it is 0.2-0.5 mass part. The content of component (e) when using modified PTFE refers to the net amount of PTFE in the modified PTFE.

<Additives>
The resin composition of the present embodiment may further contain other properties, so long as the effects of the present invention are not impaired, for example, plasticizers, antioxidants, stabilizers such as ultraviolet light absorbers, antistatic agents Additives such as mold release agents, dyes and pigments, and resins other than the above may be added. In addition, various flame retardants and flame retardant aids conventionally known, for example, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate containing crystal water. It is also possible to further improve the flame retardancy by adding a compound, a zinc stannate compound and the like.
The content of the additive may be 5% by mass or less with respect to 100% by mass of the resin composition.

<Physical Properties of Resin Composition>
-Liquidity-
The melt flow rate of the resin composition of the present embodiment is preferably 5 g / 10 min or more, more preferably 10 g / 10 min or more, from the viewpoint of further excellent fluidity. Moreover, it is preferable that it is 30 g / 10min or less from a viewpoint of dripping prevention at the time of a combustion test.
In addition, the melt flow rate of a resin composition can be measured based on ISO1133, and, specifically, it can measure by the method as described in the below-mentioned Example.

-Flame retardant-
The resin composition of the present embodiment is preferably an evaluation of V-0 and V-1 in the evaluation of flame retardancy based on the UL94-V test using an injection test piece having a thickness of 1.6 mm. More preferably, it is evaluation of V-0.
Moreover, it is preferable that it is evaluation of 5VA in evaluation of the flame retardance based on a UL94-5V test using the resin composition of this embodiment using the 2.8-mm-thick injection test piece. More preferably, it is an evaluation of 5 VA in the evaluation of flame retardancy based on the UL94-5V test using a 2.4 mm thick injection test piece.
In addition, the flame retardance of a resin composition can be evaluated by the method as described in the below-mentioned Example.

<Method for Producing Resin Composition>
The method for producing the resin composition of the present embodiment includes, for example, a method of melt-kneading each component described above using a twin-screw extruder. Examples of the twin-screw extruder include ZSK series manufactured by Copellion, TEM series manufactured by Toshiba Machine Co., Ltd., TEX series manufactured by Japan Steel Works, and the like.

  The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more and 75 or less, more preferably 20 or more, from the viewpoint of being able to knead the contained components more uniformly and obtain more excellent flame retardancy. 30 or more and 60 or less.

  The configuration of the extruder is not particularly limited. For example, the first raw material supply port upstream of the raw material flow direction, the first vacuum vent downstream of the first raw material feed port, and the first vacuum vent A second raw material supply port is provided downstream, a liquid adding pump is provided downstream of the second raw material supply port, a third raw material supply port is provided downstream of the liquid adding pump, and a third raw material supply port is provided downstream of the third raw material supply port. (2) A vacuum vent is preferably provided. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the second raw material supply port and the hydraulic pump, and a kneading section is provided between the third raw material supply port and the second vacuum vent. What provided is more preferable.

The melt-kneading temperature, screw rotation speed and the like in the method for producing a resin composition of the present embodiment are not particularly limited, and appropriately selected conditions are selected from the melt-kneading temperature 200 to 370 ° C. and screw rotation speed 100 to 1200 rpm. can do.
The melt-kneading temperature is preferably 280 to 320 ° C., and the screw rotation speed is preferably 250 to 550 rpm, from the viewpoint of causing the resin composition to exhibit excellent dripping preventing properties at the time of combustion.

  The screw configuration provided on the barrel is not particularly limited, and may be appropriately configured to provide right-handed, left-handed, orthogonal (N-type), reverse-feed (L-type) kneading disc elements, and in particular, excellent combustion. Orthogonal (N-type) kneading disc element, reverse feed (L-type) kneading disc element, 2-stroke flight from the viewpoint of expressing dripping prevention property of the first raw material supply port and the second raw material supply port Preferably, at least one screw reverse feed (left-handed winding) is provided. In addition, from the viewpoint of uniformly dispersing the inorganic filler, at least two orthogonal (N-type) kneading disc elements, at least one double flight screw reverse feed (between the third raw material supply port and the second vacuum vent) It is more preferable to provide a section including left-handed winding).

  It does not specifically limit as a raw material supply apparatus for supplying a raw material to a twin-screw extruder, For example, a single screw feeder, a twin screw feeder, a table feeder, a rotary feeder etc. are mentioned. Among these, the loss-in-weight feeder is preferable from the viewpoint that the fluctuation error of the raw material supply is small.

  When supplying a liquid raw material, it can knead | mix by feeding a liquid raw material directly into a cylinder system using a liquid adding pump etc. at an extruder cylinder part. It does not specifically limit as a liquid addition pump, For example, a gear pump, a flange type pump, etc. are mentioned. Among these, a gear pump is preferable. Furthermore, a heater or the like heats the tank that stores the liquid material used in the liquid pump, piping between the tank and the pump, piping between the pump and the extruder cylinder, etc. It is more preferable to do. Since the viscosity of a liquid raw material can be reduced by this, the load concerning a liquid addition pump can be reduced, and it is preferable from a viewpoint of operativity etc.

The method for producing the resin composition of the present embodiment is not particularly limited, but from the viewpoint of obtaining an excellent flame retardant resin composition, the total amount of the component (a) from the first raw material supply port ( The whole or a part of the b) component, the whole of the (e) component (except when the whole of the (e) component is added from the second raw material supply port), the remainder of the (b) component from the second raw material supply port However, the total amount of component (e) (excluding the case where the total amount of component (e) is added from the first raw material supply port), excluding the case where the entire amount of component (b) is added from the first raw material supply port) d) the whole or a part of the component, the whole of the component (c) from the liquid feed pump, and the remainder of the component (d) from the third raw material supply port (however, Is preferably added). Among them, regarding the addition position of the component (e), it is preferable to add from the first raw material supply port from the viewpoint of exhibiting excellent dripping preventing property at the time of combustion and appearance.
In addition, as a method of supplying the component (e) to the extruder, powder PTFE and / or modified PTFE are used, and at least one component of the components (a) to (d) is dry-blended with the PTFE in advance. It is preferred to include the step of feeding to the extruder. In particular, it includes the step of dry-blending all or a part of (a) polyphenylene ether resin in advance with the above-mentioned PTFE and supplying it to an extruder, from the viewpoint of developing more excellent dripping prevention property during burning and appearance. Is preferred.

<Molded body>
The resin composition of this embodiment can be made into a molded object by shape | molding this. The molding method is not particularly limited, but, for example, known molding methods such as injection molding, hollow molding, extrusion molding, sheet molding, film molding and the like can also be used. The molded object obtained by shape | molding the above-mentioned resin composition can be used as various molded objects, Especially, it can be used conveniently for household appliances, OA apparatus, etc. That is, the molded object of this embodiment is a molded object containing the above-mentioned resin composition.

  The molding method of the resin composition of the present embodiment is not particularly limited, and examples thereof include a method of molding using an injection molding machine. As such an injection molding machine, it does not specifically limit, For example, TOSHIBA company make, "IS100GN" etc. are mentioned.

  In the molding method of the resin composition of the present embodiment, the melting temperature, the mold temperature and the like can be appropriately selected from the ranges of 200 to 320 ° C. for the melting temperature and 30 to 100 ° C. for the mold temperature. It is not particularly limited to these.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by these examples. In addition, the used raw material is as follows.

(A) Polyphenylene ether resin (PPE)
(A-1) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.52 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
(A-2) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.41 dL / g poly (2,6-dimethyl-1,4-phenylene ether)

(B) Styrene resin (b-1) high impact polystyrene (HIPS)
Petrochemical "CT60"
(B-2) Styrene-acrylonitrile copolymer (AS)
The AS copolymer of (b-2) was produced as follows.
A mixed solution consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator is 2.5 liters / hour The solution was continuously fed at a flow rate to a 5 liter fully mixed reactor, and polymerization was carried out at 142 ° C. to obtain a polymerization solution.
The resulting polymerization solution is continuously introduced into a vented extruder, unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, and the polymer is continuously cooled and solidified, and cut into particles of styrene. Acrylonitrile copolymer (hereinafter sometimes referred to as "AS") was obtained.
The composition of the styrene-acrylonitrile copolymer was analyzed by infrared absorption spectroscopy to be 9 mass% of acrylonitrile units and 91 mass% of styrene units. In addition, the melt flow rate of this styrene-acrylonitrile copolymer was 78 g / 10 min (based on ASTM D 1238, measured at 220 ° C., 10 kg load).

(C) Phosphorus-based compounds Condensed phosphoric acid ester-based compounds, trade name "E890", manufactured by Daihachi Chemical Industry Co., Ltd.

(D) Inorganic filler (d-1) mica product name "Sozolite mica 200HK", West Japan Trade Co., Ltd. (d-2) glass fiber (GF)
Brand name "Micrograss Surface Land REV 8", manufactured by Owens Corning Japan Ltd.

(E) Modified PTFE containing 50% by mass of polytetrafluoroethylene-acrylic acid ester-methacrylic acid ester copolymer (trade name "Metabrene A3800", manufactured by Mitsubishi Rayon Co., Ltd.)

  Evaluation of the resin composition obtained by the Example and the comparative example was performed by the following method and conditions.

<Shrinkage of test piece after aging>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. From the resin composition pellet after drying, using an IS-100GN type injection molding machine (made by Toshiba Machine Co., Ltd., cylinder temperature set at 240-280 ° C, mold temperature set at 80 ° C), length 125 mm in the flow direction , A test piece with a length of 13 mm in the vertical direction and a thickness of 1.6 mm was produced.
The shrinkage of the test piece after aging the test piece at a temperature of 150 ° C. for 24 hours was determined from the following equation.
Specimen shrinkage factor [%] = ((Length of specimen in flow direction before aging [mm]-Length of specimen in flow direction after aging [mm]) / (specimen in flow direction before aging Length [mm])) × 100

<Appearance>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. From the resin composition pellet after drying, using an IS-100GN type injection molding machine (made by Toshiba Machine Co., Ltd., cylinder temperature set at 240-280 ° C., mold temperature set at 80 ° C.), length 90 mm in the flow direction A test piece with a length of 50 mm in the vertical direction and a thickness of 2.5 mm was produced.
The appearance of the test piece was visually confirmed and judged according to the following evaluation criteria.
○ (excellent): There is little floating of the filler.
((Good): The amount of floating of the filler is somewhat large.
X (Defective): The amount of floating of the filler is large.

<Melt flow rate (MFR)>
Melt flow rate (g / 10 min) was measured under the conditions of 250 ° C. and 10 kg load according to ISO-1133 using the resin composition pellets obtained in Examples and Comparative Examples.
As the evaluation criteria, it was evaluated that the larger the melt flow rate, the better the fluidity.

<Flame retardancy>
-V test-
Based on the UL94-V test, the flame retardancy was evaluated using a 1.6 mm thick injection molded test piece.
First, the resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour. The dried pellet is supplied to a screw in-line injection molding machine (trade name “IS-100GN”, manufactured by Toshiba Machine Co., Ltd.) set at 240 to 280 ° C., and injection molding is performed at a mold temperature of 80 ° C. The test piece of the dimension (length 125 mm x width 13 mm x thickness 1.6 mm) specified by the said standard was created.
The flame of a gas burner was applied to the test piece to evaluate the degree of combustion.
In addition, the flame-retardant grade showed the flame-retardant class classified by UL94-V test. Five tests were performed on all the test pieces and judged. The outline of the classification method is as follows.
V-0: Total burning time of 5 seconds or less, maximum burning time of 10 seconds or less, no flaming dripping V-1: 5 total burning time of 250 seconds or less, max burning time of 30 seconds or less, no flaming dripping

-5V test-
Based on the UL94-5V test, the flame retardancy was evaluated using injection molded test pieces of 2.4 mm thickness and 2.8 mm thickness.
First, the resin composition pellets obtained in Examples and Comparative Examples were dried at 90 ° C. for 1 hour.
The strip sample is supplied to a screw in-line injection molding machine (trade name “SH100C”, manufactured by Sumitomo Heavy Industries, Ltd.) set to 220 to 240 ° C. using dried pellets, and a condition of a mold temperature of 30 ° C. By injection molding, test pieces of the dimensions (125 mm in length × 13 mm in width × 2.4 mm in thickness and 2.8 mm in thickness) defined by the standards are prepared.
The plate sample is supplied to a screw in-line injection molding machine (trade name “SH100C”, manufactured by Sumitomo Heavy Industries, Ltd.) set to 290 to 310 ° C. using dried pellets, and a condition of a mold temperature of 100 ° C. By injection molding, a test piece of the dimensions (150 mm long × 150 mm wide × 2.4 mm thick and 2.8 mm thick) defined by the standard is produced.
The flame of a gas burner was applied to the test piece to evaluate the degree of combustion.
In addition, the flame-retardant grade showed the flame-retardant class classified by the UL94-5V test. Five short strip samples and three plate samples were tested and judged. The outline of the classification method is as follows.
5VA: In the strip sample, the total of the burning time and the glowing time after the fifth flame application was 60 seconds or less, and there was no hole opening after flame application in the plate sample.
Failure: Those that did not meet the criteria of 5 VA were rejected.

Hereinafter, a twin-screw extruder (trade name “TEM 58 SS”, manufactured by Toshiba Machine Co., Ltd.) was used as a production apparatus of a resin composition for describing each example and each comparative example in detail. In the twin screw extruder, the number of barrels is 13 blocks, and the first barrel (first supply port), the sixth barrel (second supply port), and the ninth barrel (third supply port) from the upstream with respect to the flow direction of the raw material A total of three supply ports were provided at each one), a liquid injection pump was provided at the 8th barrel, and two vacuum vents were provided at the 5th and 12th barrels. Moreover, the raw material supply method to a 2nd supply port and a 3rd supply port was taken as the method of supplying using a forced side feeder from an extruder side open port.
The screw configuration provided in the barrel and the set temperature of the barrel in the production methods 1 to 4 are as described in FIG. 1. In addition, the meaning of the symbol of the kneading disc used for the mark of the said screw structure is as follows.
・ R1: Kneading Disc Light (L / D = 1.03)
・ R2: Kneading disc light (L / D = 0.51)
・ L: Kneading disc left (L / D = 0.51)
・ N1: Kneading Disc Neutral (L / D = 1.03)
・ N2: Kneading disc neutral (L / D = 0.51)
・ Reverse: 2-stroke flight screw reverse feed (L / D = 0.39)
S: SME screw (L / D = 0.78)

[Examples 1 to 10, Comparative Examples 1 to 6]
In the twin-screw extruder set as described above, melt kneading was performed under the conditions shown in Tables 1 and 3 and under the conditions of a discharge rate of 400 kg / hour under the production conditions, to obtain pellets of the resin composition.
[Example 11]
In the twin-screw extruder set as described above, the composition was melt-kneaded under the composition and production conditions shown in Table 2 under the conditions of a discharge amount of 400 kg / hour. First, after producing a first resin composition, a second resin composition was produced using the first resin composition to obtain pellets of the resin composition.

  About each Example and comparative example, the result of having evaluated the resin composition by the above-mentioned measuring method is shown to Tables 1-3.

  As shown in Tables 1, 2 and 3, Examples 1 to 11 in which the shrinkage percentage of the test piece is 6 to 20% when aged under conditions of a temperature of 150 ° C. for 24 hours are all fluid and difficult. It turned out that it is excellent in flammability and mechanical physical properties.

  According to the present invention, it is possible to provide a resin composition excellent in appearance, fluidity, and high level of flame retardancy, and has industrial applicability as a material for home appliance / OA equipment etc. There is.

Claims (9)

(A) polyphenylene ether resin,
(B) styrenic resin,
(C) phosphorus compounds
(D) inorganic filler,
(E) polytetrafluoroethylene,
A resin composition containing
The resin composition contains 35 to 60% by mass of the component (d),
When the test piece of the resin composition prepared with dimensions of 125 mm in the flow direction, 13 mm in the vertical direction, and 1.6 mm in thickness is aged at a temperature of 150 ° C. for 24 hours, The resin composition, wherein the shrinkage factor of the test piece to be shown is 6 to 20%.
Specimen shrinkage factor [%] = ((Length of specimen in flow direction before aging [mm]-Length of specimen in flow direction after aging [mm]) / (specimen in flow direction before aging Length [mm])) × 100 With respect to a total of 100 parts by mass of the component (a), the component (b), and the component (c),
50 to 70 parts by mass of the component (a),
10 to 30 parts by mass of the component (b),
The resin composition according to claim 1, comprising 10 to 30 parts by mass of the component (c) and 0.05 to 1 parts by mass of the component (e). The component (a) is
(A-1) a polyphenylene ether resin having a reduced viscosity of 0.45 to 0.55 dL / g,
(A-2) a polyphenylene ether resin having a reduced viscosity of 0.35 to 0.45 dL / g,
Including
The resin composition according to claim 1 or 2, wherein the content of component (a-2) is 60 to 90 parts by mass with respect to a total of 100 parts by mass of component (a-1) and component (a-2). .   The resin composition according to any one of claims 1 to 3, wherein the component (d) is at least one selected from glass fibers and mica.   The resin composition as described in any one of Claims 1-4 whose said (c) component is a condensation phosphoric acid ester compound.   The molded object characterized by including the resin composition as described in any one of Claims 1-5. It is a manufacturing method of the resin composition as described in any one of Claims 1-5, Comprising:
A method for producing a resin composition, comprising the step of melt-kneading the components (a) to (e) using an extruder.   Including the step of dry blending the powdered polytetrafluoroethylene of the component (e) and / or the modified polytetrafluoroethylene with at least one of the components (a) to (d) and supplying it to the extruder The manufacturing method of the resin composition of Claim 7.   In the feeding step, dry blending of the powdered polytetrafluoroethylene and / or modified polytetrafluoroethylene of the component (e) with all or part of the component (a) is fed to the extruder. The manufacturing method of the resin composition of Claim 8 containing B.

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